Dihalophenyl alkyl carbinol pesticides



Patented Nov. 11, 1947 DIHALOPHENYL ALKYL CARBINOL PESTICIDES Robert F.Ruthruil, Chicago, 111., Oliver J. Grummitt, Cleveland, Ohio, and BertonC. Dickinson, South Bound Brook, N. J., assignors to TheSherwin-Williams Com a corporation of Ohio No Drawing. Application July28, 1945, Serial No. 607,260

18 Claims.

This invention relates to new and improved pest control compositions,more particularly insecticidal and arachnicidal compositions, andespecially to compositions which are effective as arachnicides, beingexcellent exterminators of red spider or red mite.

It is well known that there are several excellent pest control materialsavailable today, including, for example, the material commonly referredto as D. D. T., and which contains as the essential ingredient1,1-bis(p-chlorophenyl)2,2,2 trichloroethane. While this material isvery powerful, it is by no means perfect. Its action is specific and notcritical. In other words, it is extremely eiiective against some pestsand has no eilect whatsoever on others. Additionally, it kills manybeneficial insects such as honey bees as well as insects that arepredators against other harmful species. Accordingly, it is obvious thatthe use oi D. D. T. under certain circumstances may do little or nogood.

A plant may be infested by two harmful insects, one of which is keptunder control by a third predatory insect. On applying D. D. T. in suchcases one of the harmful insects and the predatory insect against theother harmful insect may be killed. As a result, the second harmiulinsect which was previously kept in check by its natural enemy thenbecomes a serious pest. This may be specifically illustrated in the caseof apples. Apple trees are infested by codling moths, aphids and redmites. The last two are more or less controlled by ladybird beetles,other predaceous insects and certain parasitic insects. The D. D. T.destroys the codling moth but at the same time destroys beneficialpredators and parasites with the result that the aphid or red mitepopulation may increase to such an extent that these pests may do asmuch or more harm than was previously caused by the codling moth.

One of the objects of the present invention is to provide a new andimproved type of pest control composition which is extremely effectiveagainst red mite, also known as red spider.

A further object of the invention is to provide new and improvedinsecticidal and arachnicidal compositions.

Another object of th invention is to provide new and improved pestcontrol compositions containlng compounds which are effective againstred mite and compatible with l,l-bis(p-chlorophenyl) 2,2,2trichloroethane. Other objects will appear hereinafter.

In accordance with the invention, it has been found that di(halophenyl)alkyl carbinols, and

pany, Cleveland, Ohio,

especially the compound di(p-chlorophenyl) methyl carbinol, are, in pestcontrol compositions, particularly effective against red mite or redspider, and also can be employed in pest control compositions containing1,1-bisip-chlorophenyl)2,2,2 trichloroethane.

The invention will be further illustrated, but is not limited, by thefollowing examples in which the quantities are stated in parts by weightunless otherwise indicated.

Example I This example illustrates the preparation of the compounddi-(p-chlorophenyl) methyl carbinol.

In a 1-liter, three-neck flask fitted with a mercury-seal stirrer, watercondenser, and dropping funnel was placed 0.25 mole of methyl-magnesiumbromide in 115 ml. of ether solution. To this was added a solution of 63g. (0.25 mole) of 4,4-dichlorobenzophenone in 700 ml. of dry benzene atsuch a rate that the ether refluxed slowly. A transient purple colordeveloped as the ketone was added. After all of the acetone had beenadded, the reaction mixture was heated with stirring on a steam bath fortwo hours, during which time a white precipitate appeared in the flask.The mixture was hydrolyzed by pouring onto a mixture of 100 ml. ofwater, 200 g. of ice and 27 g. of ammonium chloride. After separatingthe benzene-ether layer and distilling the solvent on a steam bath, 59.3g. of crude product, M. P. 64-68 degrees were recovered. This crudematerial was crystallized from 200 ml. 01' Skelly C to give 41.2 g. ofproduct, M. P. 67-685 degrees. Evaporation of the filtrate to ml.yielded 13 g. more of solid: total yield 54.2 g., 0.203 mole, 81.1%. Asecond preparation gave 53.9 g., melting 68-695 degrees, 80.7%.

A melting point determination run on a highly purified sample, using acalibrated thermometer, indicated that the melting point for thiscompound is Gil-69.5 degrees 0., uncorrected. Analyses were made whichsatisfactorily proved the structure of the compound.

Five-tenths of a gram of thecarbinol was oxidized in a solution of 2grams of chromic acid in 20 ml. of glacial acetic acid and 2 drops ofconcentrated sulphuric acid on refluxing 2 hours. After pouring themixture onto ice and crystallizing the solid from methanol, 0.3 gram oiproduct melting at 142-144 degrees C. and showing no depression in amixed melting point with authentic p,p' -dichlorobenzophenone wasobtained.

By substituting other alkyl magnesium halides in chemically equivalentproportions for the methyl magnesium bromide. the correspondingdi(pchlorophenyDalkyl carbinols were produced, including the ethyl,butyl and lauryl derivatives.

Example II Pest control compositions were prepared by dispersing thecompound of Example I in water in varying proportions, and thesedispersions were tested by spraying them on a. uitable subject infestedwith greenhouse red spider as the test animal, and observing theresults.

In this series of tests a population of all stages of greenhouse redspider was established on the upper surface of the leaves ofindividually potted Henderson baby lima bean plants, and was limited tothis surface by a ring of "tanglefoo The test material under constantagitation was applied with a precision spray gun that deliveredapproximately /3 or 1 cc.. and application of 8 shots with thisprecision sprayer represented the maximum, application without resultingin subsequent run-oil' or serious coalescing of droplets. The totalamount of liquid delivered was kept constant for all tests; thus, to aZ-shot application of test material was added 6 shots of distilledwater.

Since the purpose of this test was primarily to observe the directcontact effect 01 the materials, mortality records were taken after 48hours. In general. it may be said that the adults are more difllcult tokill than any of the nymphal stages.

The results are illustrated in the following table:

00111061111; ama 48:11am: trat on Total Total er on orf g :85;; No.0!No.0! 2 a a: Adults Nymphs sion Adults Nymphs 2 30 8" 100 100 None. 1 39406 100 100 Do. 8 26 1.086 100 100 Possib Light. 2 54. 70 if!) 100 None.

To compare the effectiveness of the diip-chlo rophenyl) methyl carbinolwith D. D. T. tests were also made with the latter as follows:

Alter 48 Hours Conocntration in N of Total Total ggfit Plant LbsJlOOshots No. oi No. of Gals. oi Adults Nymphs Dims Adults Nymphs 3D 2 22325 0 37 None. 30 8 8 N6 12 68 Do.

To determine the effectiveness 01' di(p-chlorophenyl) methyl carbinol ascompared with diphenyl methyl carbinol (i. e.. unchlorinated). testswere made in a similar manner at 8 shots or 30 pounds to the 100 gallons(200 micrograms per square centimeter). and in these tests theunchlorinated carbinoi killed only 35% red spider.

At 2 shots of 30 pounds per 100 gallons concen- Example III A series oftests was carried out in a manner similar to that described in ExampleII, on greenhouse red spider using di-(p-chlorophenyl) methyl carbinolwith the following results:

Cuncmp After 48 Hours tration in Y Total Total Per Cent LbsJlOtl ggg fNo. 0! No. of o es. of Adults Nymphs push)" Adults Nymphs a l 16 21 100None. aa 31 237 100 100 Do. 0 a 4 i5 122 100 100 D0.

Example 1V Concentra- No. of Unacoount- Per cent 'si Shots ed ForMortality 2 o a l H 3 z s 1 o Total a is l at s a 0 1 a s o o l Total l80 2 100 These tests demonstrated that di(p-chlorophenyl) methyl carbinolhad some effect in controlling the potato leafhopper.

Example V The diip-chlorophenyll ethyl carbinol was prepared in themanner described in Example I using chemically equivalent proportions ofethyl magnesium bromide instead of the methyl magnesium bromide.

Tests were conducted with an impure form of this compound to determineits eflectiveness in killing greenhouse red spider as described inExanaple II, with the results given in the following ta e:

The remaining adults we e mo ibund.

product was tested on greenhouse red spider with 2 w 18 64 the resultsgiven inthe following table:

1 o Alt us u re An additional 18% olodults were mo! band t 221 Tom Tom]Pe ecmt 1&1-

LbsJlOO No.0! No.0 Nmor tality Plant 4 159 4a 32 so gil gf 11mins Nymphssion Adults Nymphs An additional 32% of adults were moribund.

N h i 8} EB 83 it tit 89 l r o.a. 4 M 29 102 107 as 91 Non? Anadditional 30% or adults we" moribund. An additional 11% of adults weremoribund.

l 74 I48 97 100 None. 2 121 no 1 25 Do. o.s 2 m 41 4 to None. 4 181 1043s 94 Do. 15 4 105 119 a 19 Do.

An additional 34% of adults were moribund.

o.a. 4 189 ass 20 74 None. 0.3.. 1. 8 94 94 46 '94 None.

20 An additional 10% of adults were moribund. An additional 43% ofadults were moribund. I Not counted.

s or, 3B 100 None. The impure compound used in the foregoing testscorresponds to the "crude material" obtained An additional 38% adults Wmmoribum in the proces of Example I using ethyl magneslum bromide insteadof methyl magnesium bro- 3 l 103 (I) 93 we Nona. micle. A pure form ofthe compound ethyl di- (p-chlorophenyl) carbinol was also Prepared and 11 7 d tested on greenhouse red spider with the follow- B u s wmmon mgresults a 2 14a 100 100 None. 4 121 21 so no Do. Concen- After 48 Hoursifi g N0 0! Total gets]! P" gfi g Plant An additional 25% of adults weremoribund.

shots Agul is Nymphs Injury sum Adults Nymphs 0.30."... 8 10B (1) 63ill) None.

18 50 N An additional 42% of adults were moribund. 3:33;: i: 1 3 411 3 ar fill. Nvtwuntrd- 11 l 18 0 855 o. 30? i 100 1011 his??? Example VII 1so s 100 100 Serlmrs. The di(p-chlorophenyl) lauryl carbinoi wasprepared by the general method given in Example I using lauryl magnesiumbromide instead of the 3 8 167 m m 100 Non, methyl magnesium bromide,and the resultant compound was tested on greenhouse red spider. Addmonal (adults Wm mmlblmi At a dosage oi 6.6 micrograms per squarecentin a a meter a substantial kill 0! red spider was obtained n 4 2m 175 100 Mm although this material was less eilective for this purposethan the materials containing lower An additional Z]% of adults woremoribund. alkyl groups- In general, the compounds which are operable forthe purpose or this invention have the chem- 4 l" N 311.1; i it? 353 12it it". m1 formula:

011 An additional 7% oi adults were moribund. l 0.30.... 4 ii 142 4 19None. X R Y 03-.."... 8 84 45 i3 40 Do.

in which x and Y represent hydrogen or halogen A i I 30 (e. g.,chlorine, bromine or fluorine), preferably chlorine in the Dara positionof the phenyiene 3 4 82 nuclei, and R represents alkyi (e. g., methyl, Iethyl, propyl, butyl, amyi, hexyl, lauryl and Bddimm] 26% dunghomologous radicals). It will be understood that the halogen may also bepresent in the ortho or 3 a 21 95 100 Nonemeta positions, and that theinvention contemplates compositions containing mixtures of com- 1 Notcounted. pounds or this type in which the halogen is pres- Emample VIent in the para, ortho, and/or meta positions.

The n-butyl di (p-chlorophenyl) carbinol was prepared by the process ofExample I except that chemically equivalent proportions of n-butylmagnesium bromide were substituted for the methyl magnesium bromide, andthe resultant These compounds are herein referred to as the activeessential ingredients of the pest control compositions.

In the practice of the invention it is preferable to condition theactive essential ingredient by reduclng it to a particle size within therange from about 0.5 micron to 10 microns, preferably about 1 to 2microns.

It is also preferable in accordance with th invention to provide acarrier for the active essential ingredient in order that it may bedispersed properly and to increase the effectiveness. The ingredientdi(p-chlorophenyl) methyl carbinol is preferably applied to foliage orother surfaces being treated to the extent of about 1 to aboutmicrograms per square centimeter. In concentrations of 3 pounds per 100gallons of dispersion, each of the so-called shots referred to in theexamples corresponds roughly to about 2.5 micrograms per squarecentimeter. If it is desired to avoid burning the foliage it ispreferable to keep the concentration of the active ingredient, asapplied, below 20-25 micrograms per squar centimeter, although this willvary with the types of foliage.

Various types of carriers may be used, as, for example, magnesiumcarbonate and magnesium silicate. Unless the pest control composition isto be applied shortly after it is prepared the carrier should benon-acidic because we have found that carbinols of the type employedherein are unstable in the presence of acidic substances. Stabilityagainst dehydration of the carbinol is obtained by preparing pestcontrol compositions which are substantially non-acidic. The particlesize of the carrier and the active essential ingredient is preferablyaround 1 to 2 microns. They may be intimately mixed or blended in anysuitable manner.

The proportion of the carrier and active essential ingredient may varyrather widely, but for most practical spray purposes equal proportionsby weight of carrier and the active essential ingredient have been foundto be suitable. In general, the proportions of the active essentialingredient are preferably within the range of 25% to 75% of the totalweight of the carrier and said ingredient. In some cases it is desirableto add to the carrier-(ii(chlorophenyD alkyl carbinol mixture about 0.5to about by weight of an anti-bonding agent such as talc.

If the pest control composition is to be applied as a spray, a mixtureof a carrier such as ma nesium carbonate and the active essentialingredient will give good results. If desired, a wetting agent can beadded, for example, lauryl sulfate, although in some instances wettingagents of this type are undesirable because the composition after beingapplied is more readily dispersed by rainfall. Other types of wettingagents which may be employed are volatile wetting agents such asmorpholine.

The compositions of this invention can also be prepared in solventsolutions such as naphtha, or 011 solutions, or mixed with water to formemulsions. Another type of composition which can be prepared inaccordance with the invention is one in which the active essentialingredient is dispersed in a liquid capable of expanding rapidly toatomize the composition. A composition of this type, for example, maycontain up to 5% of the active essential ingredient, up to 10% ofacetone or cyclohexanone, which acts as a coupling agent to increase thesolubility of the essential ingredient, up to 10% of an oil such as amineral oil or vegetable oil which serves to resulate the particle size(smaller particles beinl; produced with less 011) and the remainder asolvent capable of expanding rapidly at ordinary temperatures to form agas as, for instance, difluorodichloro methane or methyl chloride.

The effective concentrations for field use of the active essentialingredient may vary somewhat, but are preferably within the range of0.25 to 0.5 pound per gallons of dispersion with the preferred amountbeing about 0.4 pound per 100 galions.

An important feature of the invention is the provisions of a new andimproved pest control composition comprising as one of the activeingredients a bisichlorophenyl) polychloroethane of the type describedin U. S. Patent 2,329,074, more particularly l,1-bis(pchlorophenyl)2,2,2trichloroethane, and a compound of the type herein described, moreparticualrly di-p-chlorophenyl) methyl carbinol. While the proportionsof these two ingredients may vary, a typical composition provided inaccordance with the invention may contain from about pound to 1 poundper 100 gallons of water of 1,l-bis(p-chlorophenyl) 2,2,2,trichloroethane and a ratio of di(p-chlorophenyl) methyl carbinol:i,l-bis(p-chlorophenyl)2,2,2 trichloroethane within the range from 1:10to 1:1, calculated in parts by weight.

The pest control compositions provided herein have the advantage thatthe active essential ingredients are colorless, stable and have a verylasting effect due to their low vapor pressure under the conditions ofuse. comparatively few compositions are known today which are effectiveagainst red spider or red mite, and some of the combinations which aremost widely used have the disadvantage that they stain not only thesurface being treated but also the operator.

The present invention also provides a type of pest control compositionwhich kills red spider or red mite as well as certain other types ofinsects without killing the predatory insects, such as the ladybirdbeetle. The compositions of the invention which contain chlorinateddiphenyl chloroethanes will, of course, also kill the predatory insects,but they have the advantage as compared with the D. D. T. type ofcomposition heretofore in use, that they also kill red mite or redspider. This pest, therefore, does not continue to multiply as has beenthe case in the previous usage of D. D. T. The compositions of thepresent invention will not destroy the foliage when employed in therecommended amounts. On the other hand, the D. D. '1. type ofinsecticide alone may have some tendency to produce some marginal orspot burning of the foliage. Continued use of D. D. T. alone, as alreadyexplained. brings about a severe mite infestation which in turn causes asevere "bronzing" of foliage. This will vary considerably, dependingupon the type of foliage which is being treated.

Having thus described the invention, what we claim as new and desire tosecure by Letters Patent of the United States is:

1. A pest control composition comprising es sentially a compound havingthe general formula:

in Q i G x a v in which X and Y represent halogen, and R is alkyl.

2. A pest control composition comprising essentially a compound havingthe general formula:

on G Hl which is a non-staining white solid with a melting point, whenpure, of 69-695 degrees 0., and

2,4so,sse

is flu-ther characterized by stability and low vapor pressure underordinary conditions.

3. A pest control composition comprising essentially a compound havingthe general formula:

$33! 4. A pest control composition comprising essentially a compoundhaving the general formula:

in K i v in which X and Y represent halogen, and R is alkyl. conditionedto a particle size within the range from 1 to microns.

5. A pest control composition comprising a compound or the generalformula:

in which X and Y represent hydrogen or halogen and R is alkyl, and acarrier therefor.

6. A pest control composition comprising a compound or the formula:

$8; and a carrier therefor.

7. A pest control composition comprising the compound and a carriertherefor.

8. A non-acidic composition comprising a. compound oi the generalformula:

in X i y in which X and Y represent hydrogen or halogen and R is alkyl,and a non-acidic carrier therefor.

9. A non-acidic composition comprising a compound of the formula:

and a non-acidic carrier therefor.

10. A non-acidic composition comprising the compound Oi O and anon-acidic carrier therefor.

11. An arachnicidai composition comprising as an active essentialingredient the compound on o c and a non-acidic carrier therefor, theproportion of the active essential ingredient being within the range oiabout 25% to about 75% of the total weight 01' said ingredient and saidcarrier.

12. A dusting composition comprising as an active essential ingredientthe compound on (HO-$G-Cl JJH; as the active essential ingredient, and anonacidic carrier therefor, the particle size of said carrier and saidactive essential ingredient each being within the range or about 0.5 to10 microns. 14. A pest control composition comprising the compound on0K3 as an active essential ingredient, an approximately equal proportionby weight 01' magnesium carbonate, and about 0.5 to about 10% by weightof talc, based on the weight or total solids.

15. A method of destroying red mite which comprises applying thereto acompound of the general formula in K i 1? in which X and Y representhydrogen or halogen, and R is alkyl.

16. A method oi destroying red mite which comprises applying to thefoliage of vegetation,

subject to infestation by red mite, a compound of the formula on t D Qin which R is alkyl.

17. A method of destroying red mite which comprises applying thereto acompound of the formula on 0*0 I H;

18. A method of destroying pests, including red mite, which comprisesapplying thereto a composition containing a bis(chlorophenyl)polychloroethane and a compound having the general formula QiQ

wherein X and Y represent hydrogen or halogen, and R is alkyl.

ROBERT F. RUTHRUFF. OLIVER J. GRUMMITT. BERTON C. DICKINSON.

(References on following page) 11 l2 anemone crrsn Number Name nm Thefollowing references are of record in the 30-33-700 11 1 Dec. 1. 1M fileof this patent: .707.181 Weiler et a1. Ml N. 1

UNITED STATES PATENTS 5 OTHER one Number Name i Date Bellsteln,Hanrlbuch der Oreanlschen Chcmle 2,005,797 Moore June 25. 1935 1928edition. volume 6. Co 1 Paton om 2,248,543 for Horst May 2'1, 1941brary. P. 885. p, n t a u 3,329,074 Muller Sept. 7, 1943 10 Certificateof Correction Patent No. 2,430,586. November 11, 1947.

ROBERT F. RUTHRU'FF ET AL.

It is hereby certified that errors appear in the rinted specification ofthe above numbered patent requiring correction as follows: olumn 2, line23, Example 1, for the word acetone" read ketone; column 8, line 8, for"provisions read provision: line 14, for particualrly" readparticularly; column 9, line 39, claim 7, strike out "compound andinsert the same after comprising the" in line 33, same claim; and thatthe said Letters Patent should be read with these corrections thereinthat the same may conform to the record of the case in the PatentOfiice.

Signed and sealed this 17th day of February, A. D. 1948.

THOMAS F. MURPHY,

Am'ltant Commissioner of PM 11 l2 anemone crrnn Number Name nm Thefollowing references are of record in the 30-33-700 11 1 Dec. 1. 1M fileof this patent: .707.181 Weiler at I. Ml N. 1

UNITED STATES PATENTS 5 OTHER REFERENCES Number Name i Date Bellsteln,Hanrlbuch der Orunlschen Chcmle 2,005,797 Moore June 25. 1935 1928edition. volume 6. Copy in Patent Ofllce Li 2,248,543 t'er Horst May2'1, 1941 brary. P. 885.

3,829,074 Muller Sept. 7, 1943 10 Certificate of Correction Patent No.2,430,586. November 11, 1947.

ROBERT F. RUTHRU'FF ET AL.

It is hereby certified that errors appear in the rinted specification ofthe above numbered patent requiring correction as follows: olumn 2, line23, Example 1, for the word aoetone" read ketone; column 8, line 8, for"provisions read provision: line 14, for particualrly" readparticularly; column 9, line 39, claim 7, strike out "compound andinsert the same after comprising the" in line 33, same claim; and thatthe said Letters Patent should be read with these corrections thereinthat the same may conform to the record of the case in the PatentOfiice.

Signed and sealed this 17th day of February, A. D. 1948.

THOMAS F. MURPHY,

Am'ltant Commissioner of PM

